Metal acetate-acidic catalyst system for cellulosic fabric treatment

ABSTRACT

High strength losses in cellulosic fabrics when treated by a pad, dry and cure technique with nitrogen-containing creaseproofing agents to produce durable press properties are avoided by eliminating a major part of the usual acidic catalyst and adding at least an equal amount of zinc acetate or aluminum acetate.

O United States Patent 1 1 3,634,019 72] inventors Warren L. Beaumont [5 6] References Cited sahsbm'yi UNITED STATES PATENTS xi Charm 3,186,954 6/1965 Hushebeck 117/1394 x 3,243,252 3/1966 Hushebeck.... 8/1 15.6X [21] P 667671 3,084,071 4/1963 vah L00 et al. 117/1394 x [22] 1967 3 139 322 6/1964 Hushebeck 8/1 16 3 [45] patented Jan- 1972 [73] Assignee Proctor Chemical Company, Inc. OTHER REFERENCES Salisbury, N.C. F rick et al., Effects of Cross-Linkage in Wrinkle-Resistant Cotton Fabrics," Textile Research Journal, Vol. 30, No. 7, July, 1960, pages 495- 497. Primary Examiner-George F. Lesmes Assistant Examiner-John R. Miller 54 METAL ACETATE-ACIDIC CATALYST SYSTEM Mame? Kemmh Palmer and Estabrk FOR CELLULOSIC FABRIC TREATMENT 5 Drawmgs ABSTRACT: High strength losses in cellulosic fabrics when [52] U.S. Cl 8/ll6.3, treated by a pad, dry and cure technique with nitrogen-con- 38/l44, l17/l39.4,260/29.4R taining creaseproofing agents to produce durable press pro- [51] Int. Cl D06m 13/12, perties are avoided by eliminating a major part of the usual D06m 13/34 acidic catalyst and adding at least an equal amount of zinc [5 8/1 16.3 acetate or aluminum acetate.

Field of Search BACKGROUND OF THE INVENTION 1. Field of the Invention Treatment of cellulosic fabrics, particularly cotton textiles, to improve wrinkle resistance and create durable press characteristics, i.e., production of so-called wash and wear fabric articles, is a highly developed art. Although a number of procedures have been investigated and in some cases commercially developed, the majority of fabric treatments for creating durable press fabric articles employ the so-called pad, dry and cure process which is now standard in the textile industry. A recent modification of this procedure involves pretreatment with the creaseproofing agent followed by drying and conversion of the impregnated dried fabric to a finished garment before completion of the curing operation which creates the final durable press properties, i.e., the so-called postcure or delayed cure technique. The problems of strength loss, curing conditions and the like are more acute with the postcure procedures as compared to the older immediate cure operation.

The present invention is concerned with fabric treating operations which are improvements on all such general prior known methods of treating fabrics with aqueous solutions of nitrogen-containing creaseproofing agents in the presence of catalysts designed to accelerate the curing step performed at elevated temperatures.

The textile industry has been burdened with a serious problem in the prior known methods of finishing cellulosic fabrics with the creaseproofing agents in the manner referred to above due to the high strength losses which occur in the fabric as a result of these treatments. Detrimental effects to the fabric appear as loss both in tensile strength and abrasion resistance. Although various suggestions have been made for mitigating the strength losses in the fabric in such treatments, the roblem continues to be of great concern to the textile industry and, in fact, has virtually prevented the use of these treatments on 100 percent cotton fabric, i.e., fabrics which are made entirely of cotton fibers or yarns. Thus, in order to be able to market garments having sufficient strength after being subjected to such durable press treatments, the textile industry has employed blended fabrics which contain large amounts, e.g., 25 to 75 percent, of synthetic fibers such as polyester fibers, nylon fibers and the like, which are uneffected by the creaseproofing treatments. However, the presence of the synthetic fibers in many cases is undesirable. For example, the blended fabrics tend to be more expensive than 100 percent cotton fabrics. Also, since the creaseproofing treatment affects only the cellulosic content of the fabrics, the over all effect in durable press production is reduced as compared with that which could be obtained with 100 percent cotton fabrics if it were not for the high strength losses occasioned by the durable press treatments. Additionally, the presence of the synthetic fibers tends to increase soiling, staining and crocking of the fabrics so that it is more difficult to maintain a clean and unmarred appearance to the blended fabrics although they may be improved in wrinkle resistance. The problem is acute today in the textile industry because of the great demand by consumers for fabrics and garments which have the minimum care aspects of durable press treatments. However, the high levels of creaseproofing agent content required to meet the rigid requirements for such fabrics has made it necessary to blend synthetic fibers and cotton resulting in the blend fabrics containing as high as 75 percent of the synthetic fibers in order to overcome the strength loss normally associated with the creaseproofing treatments. The industry, therefore, has a very definite need for improved methods and/or compositions which can be used for the treatment ofcellulosic fabrics and in particular for the finishing of 100 percent cotton fabrics, to impart a finish which meets the rigid requirements of durable press garments as they are now expected by consumers, at the same time providing substantial improvement in strength properties in the final treated fabric article.

DESCRIPTION OF THE PRIOR ART Early in the development of creaseproofing of textiles, reaction products of urea with formaldehyde were employed as the active creaseproofing agent (U.S. Pat. No. 2,808,341). Such urea-formaldehyde resins were used not only for the production of flat fabrics having wrinkle-resistant characteristics but also in postcure operations in which permanent pleats or other shapes were imparted permanently in the fabric US. Pat. No. 2,769,584) as well as the impartation of durable press to finished garments (U.S. Pat. No. 2,974,432).

The nitrogen-containing organic creaseproofing agents, such as urea-formaldehyde resins, initially used in these textile treatments were subsequently found to create strength loss problems in garments after bleaching with chlorine-containing bleaching solutions due to chlorine retention by the treating agents which, upon hot pressing, ironing, or the like, tended to liberate hydrochloric acid at elevated temperatures which degraded the fabrics. This led to the development of reaction products of cyclic ureas with formaldehyde as the creaseproofing agents (U.S. Pat. Nos. 3,220,869 and 3,216,780). Triazone ring compounds (U.S. Pat. Nos. 2,321,989 and 2,950,553) as well as other nitrogen-containing organic compounds (U.S. Pat. No. 2,819,179) have been suggested, and in some cases commercially employed, as creaseproofing agents for textiles. The present invention concerns operations in which any of these prior known type of organic nitrogen-containing creaseproofing agents are used in the treatment of textile fabrics to impart wrinkle-resistant properties.

Acidic materials, particularly Lewis acid compounds such as hydrochloric acid, aluminum chloride, zinc chloride, zinc nitrate and the like, are generally employed in conjunction with the nitrogen-containing creaseproofing agents in order to produce a socalled cure" of the treating agent. This may be actual resin formation where the creaseproofing agent is of a resin forming type, e.g., urea-formaldehyde resins, or nonresinous where the agent is not resin forming, but reactive with cellulose as in the case of the methylol ethylene urea and similar cyclic ureas. In an attempt to improve this class of textile treating operation, other materials serving as catalysts for the curing operation have been suggested and investigated, such as alkaline earth metal salts (U.S. Pat. No. 2,142,623) and magnesium chloride (U.S. Pat. No. 2,846,337). Aluminum salts of various acids have also been suggested for socalled spontaneous cure techniques which are performed at low temperature for times of the order of several hours (U.S. Pat. No. 3,084,071). Zinc chloride and zinc nitrate are acidic materials employed widely as catalysts in the trade for curing at elevated temperatures and short curing times US. Pat. No. 2,709,141

OBJECTS A principal object of this invention is the provision of new improvements in fabric treating methods, products and compositions to impart durable press properties to fabrics while mitigating strength losses in the treated articles.

Further objects include the provision of:

1. New creaseproof agent compositions for use in the production of durable press fabrics which overcome high strength loss in the treatment of cellulosic fabrics.

2. New fabric wrinkleproofing operations which retain sufficient original strength of a percent cotton fabric to allow such fabrics to be treated with high levels of creaseproofing agent.

3. New durable press fabric treatments which may be used without substantial degradation in strength properties on l00 percent cotton fabrics or cotton and rayon blends which could not otherwise endure the strength loss usually accompanied by so-called resin finishing, e.g., fabrics such as corduroys, flannels, sheeting fabrics, lightweight denims, interlining cloth, and the like.

4. Improvements in treating fabrics to provide durable press characteristics useable with postcure techniques that employ relatively high temperatures, e.g., l50l80 C., which eliminate overcuring problems and excessive loss in fabric strength.

Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

SUMMARY OF THE INVENTION These objects are accomplished, in part, by reduction in the amount of conventional acidic catalyst used in an aqueous treating liquor containing a nitrogen-containing creaseproofing agent and inclusion of at least an equal amount, based upon the weight of the acidic catalyst, of a metal acetate selected from the group zinc acetate, aluminum acetate and mixtures thereof.

Advantageously the metal acetate is present in the aqueous treating liquor in such amount that the weight ratio of creaseproofing agent to metal acetate is between about 25:1 and 1:1 and the creaseproofing agent constitutes 5 to 30 percent by weight of the aqueous treating liquor.

The invention is most advantageously used with aqueous treating liquors that contain a Lewis acid compound selected from the group consisting of zinc nitrate, zinc chloride, magnesium chloride and mixtures thereof with the weight ratio of the Lewis acid compound to metal acetate being between 1:100and 1:1.

Basically fabric treating methods performed in accordance with the invention comprise:

A. Providing an aqueous treating liquor comprising:

a. nitrogen-containing fabric creaseproofmg agent having a plurality of cellulose reactive groups selected from the group consisting of methylol groups and etherified methylol groups,

b. the metal acetate and c. the Lewis acid compound,

B. impregnating a cellulosic fabric with said aqueous treating liquor and C. drying and heating the fabric carrying said creaseproof ing agent and catalyst to an elevated temperature between about 90-200 C. sufficient to cure the creaseproofing agent.

The foregoing objects are also, in part, accomplished by the provision of new aqueous fabric treating compositions comprising:

A. nitrogen-containing organic fabric creaseproofing agent containing a plurality of cellulose reactive groups selected from the group consisting of methylol groups and etherified methylol groups,

B. metal acetate selected from the group consisting of zinc acetate and aluminum acetate, the weight ratio in said composition of said creaseproofing agent to said metal acetate being between 25:3 and 5:4, and

C. a Lewis acid compound selected from the group consisting of zinc nitrate, zinc chloride, magnesium chloride and mixtures thereof in which the weight ratio of the Lewis acid compound to said metal acetate is between 1:100 and 1:1. Advantageously, the total solids content of the aqueous treating liquor is between about 5 and 50 percent and the amount of creaseproofing agent in the liquor amounts to between about 5 to 30 percent.

EXAMPLES The following details of operations in accordance with the invention and reported data illustrate the further principles and practice of the invention to those skilled in the art. In these examples and throughout the remaining specification and claims, all parts and percentages are by weight and all temperatures are in degrees centigrade unless otherwise specified.

EXAMPLE 1 Separate portions of white sheeting fabric made 100 percent of cotton fibers were treated with aqueous treating solutions of the following composition:

dimethylol ethyl carbamate 4% 8% dimethylol triazine 0.8% dimethylol ethylene urea 3.2% ZnCl, 0.75% M CI,-6H,O 4% ZntC, H O, ),'2H,O 4%

water 87.25% 88% Composition (2) is a typical commercial formula used as a control to compare physical properties of the finishes.

With each solution, application was made by a standard pad, dry and cure process, the padding being performed with a roller pressure adjusted to give percent wet pickup. The curing was done at 180 C. for 1 minute. Small test samples were cut from the finished fabric and subjected to standard industry tests to evaluate various properties. The resulting average values are reported in the following table:

TABLE I Wash wear appearance Crease angle AATCC AATCC-66- Tenslle 1959'1, degree strength g. O1. 1 5 W F W F Ref. R. wash washes Treatment:

EXAMPLE 2 Separate portions of percent cotton playtime denim fabric were treated with aqueous treating solutions containing the following percentage of ingredients dissolved in water:

dimethylol triazine 1.5% 1.5% 1.5% dimethylol ethylene urea 6.0% 6.0% 6.0%

MgCl,'6H,O 3.5% nonionic wetting agent 0.1% 0.1%

aluminum acetate 4% Zn (N h 0.5%

Zn cl 0.5% buffered aluminum acetate 2% The buffered aluminum acetate was a commercial product sold under the trade name Niaproof identified as Al(Ol-l C H O l/3H BO The composition (3) is a typical commercial formulation used as a control run. The solutions were padded on to give 80 percent wet pickup. The fabric was then dried and cured at C. for 1.5 minutes.

Evaluation tests on the resulting treated fabric yielded the results reported in the following table:

Separate portions of 100 percent cotton corduroy fabric were treated with aqueous solution containing the following percentage of ingredients dissolved in water:

Composition (7) is a typical commercial formulation used for comparison purposes.

The solutions were padded on the fabric portions to give 80 percent wet pickup. Then the fabric was dried, cut into suitable pattern, sewn into simulated pants cuffs and pressed. These were then given a post curing at 150 C. for 10 minutes. The results showed that the methods of this invention have a decided advantage for postcure operations since the relatively mild nature of the catalysts employed result in little or no precuring taking place in drying or storage of the treated and dried fabric prior to fabrication into garments and postcuring. This is in addition to the critical improvement in strength properties over the conventional finish as shown by the following data:

This example illustrates the use of the new fabric treatments with a low level formulation on a lightweight print cloth that initially only had 28 pounds filling tensile strength. The treating solution given in solids dissolved in water was:

4.0% Dihydroxy Ethylene Urea Dimethylol Derivative 1.5% Zinc Acetate Dihydrate 0.5% Zinc Chloride.

The fabric was impregnated and squeezed to a wet pickup of approximately 80 percent, dried at 150 C. and cured at 170 C. for 1% minutes. This treatment produced a wash/wear quality of 4.7 as measured by the Eastman overhead method. The tensile strength was 22 pounds in the filling, having lost only 6 pounds or 21 percent of the original tensile. Treatments by conventional resin/catalyst systems capable of producing wash/wear in this high degree usually sacrifice the order of 50 percent of the original tensile strength.

EXAMPLE 5 A fabric treatment according to the invention was performed using a high level of impregnation, with the following treating solution based on solids dissolved in water:

12.5 Dihydroxy Ethylene Urea Dimethylol derivative 3.8% Zinc Acetate Dihydrate 1.5% Zinc Chloride.

The fabric involved was 136X64 all cotton white broadcloth having an unfinished tensile strength of 55 pounds in the filling. The fabric was impregnated at percent wet pickup, dried at C. and cured at C. for 1% minutes. As a control, the identical fabric was treated with a conventional formulation in the same way, the formula being on a solids ba- 12.5% Dihydroxy Ethylene Urea Dimethylol Derivative 2.5% Zinc Chloride Test evaluation of the results of the'two treatments resulted in the following data:

Invention Formulation Conventional Formulation Crease Angles 292 283 W F W F Tensile 57.8 lbs. 36.4 lbs. 45.0 lbs. 28.0 lbs. Tear 605 g. 547 g. 416 g. 419 g.

1 Wash 5 Washes 1 Wash 5 Washes Wash/Wear (Eastman Overhead System) 4.2 4.2 4.2 4.2

It is to be noted that the loss in filling tensile using the invention technique was only 35 percent where the conventional system, for no better creaseproofing performance, lost 50 percent of the original filling tensile.

DISCUSSION OF DETAILS The new fabric treating methods described herein are particularly advantageous with fabrics made entirely of cotton, i.e., 100 percent cotton fabric, or mixtures of cotton with other cellulosic fibers, e.g., viscose rayon, linen and the like. This is in large measure due to the fact that high strength losses which have occurred in the prior known methods for production of durable press fabrics have not been usable on a commercial scale with sucg 100 percent cellulosic fiber fabrics. However, although the improved strength characteristics of fabrics treated in accordance with the new methods is not as great with blend fabrics made in part with cellulosic fibers and in part from synthetic fibers such as polyester fibers, nylon fibers or the like, the new procedures may, if desired, be utilized in connection with such blend fabrics.

The new textile treating methods described herein are advantageously performed under neutral or relatively mild acidic conditions, i.e., at a pH preferably in the range of about 6 to 7. This is to be contrasted to creaseproofingv treatments which are conducted under relatively strong acid conditions, e.g., pHs of the order of 3 to 4, and which necessitate fabric handling at relatively low temperatures such as below 60 C. and extended curing times of the order of several hours or more (see US. Pat. No. 3,084,071). In order to obtain the preferred pH conditions for use in the new operations, one may resort to a balancing of the metal acetate and Lewis acid compound ratio within the general ranges previously recited in order to give the advantageous pH condition. With standard nitrogen-containing creaseproofing agents such as the dimethylol cyclic ureas and using a curing system consisting of zinc acetate dihydrate and zinc chloride, the advantageous pH conditions may be obtained for a variety of creaseproofing agent concentrations as illustrated by the following table:

% DMEU Zinc Acetate Dihydrate Zinc Chloride There can be considerable latitude in the quantity of metal acetate used in accordance with the procedures herein related depending upon the specific Lewis acid compound employed as part of the curing system and, as illustrated above, by the creaseproofing agent concentration of the treating liquor. A skilled operator performing the new operations can, however, by simple testing, determine optimum relative proportions of the metal acetate and Lewis acid compound necessary in each individual case to provide the advantageous pH condition of about 6 to 7.

The new treating methods are applicable to any type of cellulosic fiber containing fabric including woven, knit and nonwoven fabrics. The beneficial effects of the new operations will be much more apparent, however, with fabrics which are rather low in tensile strength to begin with and which consequently cannot endure strength losses usually accompanied by durable press finishing. Hence, particular advantage can be obtained from the new operations in conjunction with 100 percent cotton fabric or cotton-rayon blend fabrics of lightweight construction including corduroys, flannels, sheeting fabrics, lightweight denims, interlining cloths and the like.

From the foregoing examples and description, it can be seen that the new methods for treatment of cellulosic textiles broadly comprises impregnating a fibrous web with a solution comprising a nitrogen-containing creaseproofing agent and an acidic catalyst system formed of a combination of a Lewis acid compound and a metal acetate selected from the group consisting of zinc acetate, aluminum acetate, and mixtures thereof, drying the impregnated fabric and then heat curing the fabric at an elevated temperature between about 90 to 200 C. sufficient to cure the creaseproofing agent either at the textile treating plant as a step in the fabric treating or in a postcuring operation at some removed location following cutting, sewing, and similar operations in the formation of a garment.

The methods and compositions of the invention contemplate use of any nitrogen-containing organic creaseproofing agent known to be useful in the treatment of textile materials in the production of wash and wear, durable press or comparable textile dimension stabilizing procedures. Specific examples of nitrogen-containing compounds usable as the creaseproofing agents in accordance with this invention include:

urea-formaldehyde reaction products l-methyl-3,5-dimethylol-2,6-dihydrotriazine-4 one melamine-formaldehyde reaction products biscarbamate-formaldehyde adducts (US.

l-chloromethyl-3,5-dimethylol-2,6-dihydrotriazine-4 one dimethylol dicarbamate dimethylol dihydroxy ethylene urea l-benzyl-3,5-dimethylol-2,6-dihydrotriazine-4 one glyoxalmonoureines methylol adducts of dicyandiamides polymethylol guanidine and derivatives polymethylolbutanediol diurethane dimethylol butyl triazinone dimethylol adipic acid diamide N-methylolacrylamide and derivatives propylene urea-formaldehyde adducts tetramethylol glyoxal diureine dimethylol N-ethyl triazone tetramethylol dimethyl acetylene diurein polymethylol N alkyltriazones dimethylol formamide dimethylol 5-hydroxy-tetrahydro-2(lH)oxopyrimidine It is preferred to use those nitrogen-containing organic creaseproofing agents which are soluble in water to an extent of at least grams per liter of water and to form the treating compositions for use in the invention by dissolving the creaseproofing agent in water along with the indicated acidic catalyst system.

In addition to the metal acetate component as previously stated, the catalyst systems of the invention will include a Pat. No.

Lewis acid compound known to be useful in catalyzing the curing of nitrogen-containing organic creaseproofing agents. Zinc nitrate, zinc chloride and magnesium chloride, or mixtures thereof are preferred as Lewis acid compounds for use in these new operations. However, other usable Lewis acid compounds include free acids such as sulfuric, hydrochloric. pyrophosphoric, phosphoric, chloroacetic and like acids or acidic salts including aluminum chloride, sodium bisulfate, zirconium oxychloride, and the like. If for some particular reason consideration might be given to the use of other acidic materials for use as components of the catalyst systems, a brief test with such similar contemplated acidic material will quickly reveal the effectiveness of the material for the contemplated operation.

The amount of catalyst material used in the new treating procedures may be varied depending, at least to some extent, upon the creaseproofing agent used and the combination of metal acetate and Lewis acid compound used as the catalyst system. A convenient way of prescribing the amount of catalyst components is by reference to the quantity of creaseproofing agent used. Advantageously, the proportion of metal acetate and Lewis acid compound are balanced so that the aqueous treating liquor applied to the fabric will have a pH between about 6 and 7 although it would not be outside the range of operations contemplated by the invention to operate beyond this pH range. With reference to the creaseproofing agent, the quantity of metal acetate employed will be such as to provide a weight ratio of creaseproofing agent to metal acetate between 25:3 and 5:4. in turn, the quantity of Lewis acid compound can be prescribed in terms of the amount of metal acetate, i.e., a weight ratio of Lewis acid compound to metal acetate between 1:100 and lzl. in some cases, it may be desirable to include additional buffering salts or the like, e.g., calcium chloride, sodium chloride, sodium fluoride, etc.

The amount of the active creaseproofing agent andin turn the quantity of aqueous treating liquor applied to the fabric may be varied and will depend to some extent upon the particular reactants employed, the time and temperature conditions most suitable for plant operation and the nature of the fabric being treated, e.g., the weight, thickness, number of folds that may be in a formed garment and the like. By way of example, with procedures where finished garments which may have several thicknesses of cloth are subjected to postcuring, operations are generally performed at lower temperatures and more extended times in order to insure that all sections of the garment become treated without surface scorching or the like. The optimum quantity of treating agent and temperature or other operation conditions may be readily determined by a few trial operations utilizing the principles of the invention as disclosed. Treating solutions containing 5 to 30 percent active creaseproofing agent and up to 50 percent solids content have been found useful, i.e., for the aqueous treating liquors, the creaseproofing agent and catalyst system are dissolved in 60 to percent water.

Effective results of the treatments are obtained if about I to 25 percent based upon the weight of the dry fabric, of nitrogen-containing organic creaseproofing agent is applied to the fabric. Advantageously, about 5 to 15 percent is applied. Such quantities of treating reagent in the fabric can be obtained by impregnating the fabric with sufficient treating liquor to give about 50 to I50 percent wet pickup and advantageously between about 50 to percent.

Conventional procedures may be employed for applying the aqueous treating liquors to the fibrous web and there are many types of commercially available devices that can be used for this purpose. However, special procedures or equipment may be employed if desired. For the most part, the application of the treating liquors can be accomplished by established padding or impregnation procedures using standard textile processing equipment. Alternatively, however, it is possible to apply the liquors in any other suitable fashion, such as spraying, roller coating, brushing, or the like.

Following the impregnation, the fabric is dried, e.g., by heating at a temperature between 90 and 200 C. for about 1 to 30 minutes, shorter times being generally used for the higher temperatures. lfa postcure procedure is to be followed, care should be exercised to prevent substantial curing or reaction of the creaseproofing agent with the textile during the drying step. Curing of the impregnated fabric is advantageously accomplished at a temperature in the range of 90 to 200 C. for times varying between seconds to 15 minutes, the tures and vice versa. Such drying and curing operations may be accomplished in hot air ovens, with infrared radiation, high-frequency radiations or other heating methods known in the art.

The new procedures may be used in conjunction with other textile processing operations if this appears desirable or advisable taking into the account the nature of the fabric, the proposed end use and the like. Examples of such additional operations include mothproofing, waterproofing, mechanical procedures such as embossing, pleating, pressing, and the like, or the application of other treating agents. In this latter category, there may be applied simultaneously or in conjunction with the new treating liquors such adjuvants as softeners, lubricants, water-repellent agents, mothproofing agents, mildewproofing agents, sizing agents, dyes, pigments, and the like.

The embodiments of the invention in which an exclusive property or right is claimed are defined as follows:

1, A process for improving cellulosic textile fabric which comprises:

A. providing an aqueous treating liquid comprising:

a. 5 to 30 percent by weight of nitrogen-containing organic fabric creaseproofing agent having a plurality of cellulose reactive groups selected from the group consisting of methylol groups and etherified methylol groups,

longer times being employed with lower tempera- 1 b. metal acetate selected from the group consisting of zinc acetate, aluminum acetate and mixtures thereof, the weight ratio of said creaseproofing agent to said metal acetate being between about 25:1 and 1:1, and

c. an acidic catalyst selected from the group consisting of zinc nitrate, zinc chloride, magnesium chloride and mixtures thereof, the weight ratio of said catalyst to said metal acetate being between about 1:100 and 1:1,

B. impregnating a cellulosic fabric with said aqueous treating liquid, and

C. drying and heating the fabric carrying said creaseproofing agent, catalyst and metal acetate to an elevated temperature between about -200 C. sufficient to cure the creaseproofing agent.

2. The process of claim 1 wherein the weight ratio of said agent to said metal acetate is between 25:3 and 5:4.

3. The process of claim 1 wherein the textile fabric is percent cotton fabric.

4. A textile fabric made by the process ofclaim l.

5. A composition for improving cellulosic textile fabric by impregnation followed by drying and curing at elevated temperatures which comprises:

A. nitrogen-containing organic fabric creaseproofing agent containing a plurality of cellulose reactive groups selected from the group consisting of methylol groups and etherified methylol groups, and

B. metal acetate selected from the group consisting of zinc acetate and aluminum acetate, the weight ratio in said composition of said creaseproofing agent to said metal acetate being between 25:3 and 5:4.

C. a Lewis acid compound selected from the group consisting of zinc nitrate, zinc chloride, magnesium chloride and mixtures thereof, the weight ratio ofsaid Lewis acid compound to said metal acetate being between 1:100 and 1:1. 

2. The process of claim 1 wherein the weight ratio of said agent to said metal acetate is between 25:3 and 5:4.
 3. The process of claim 1 wherein the textile fabric is 100 percent cotton fabric.
 4. A textile fabric made by the process of claim
 1. 5. A composition for improving cellulosic textile fabric by impregnation followed by drying and curing at elevated temperatures which comprises: A. nitrogen-containing organic fabric creaseproofing agent containing a plurality of cellulose reactive groups selected from the group consisting of methylol groups and etherified methylol groups, and B. metal acetate selected from the group consisting of zinc acetate and aluminum acetate, the weight ratio in said composition of said creaseproofing agent to said metal acetate being between 25:3 and 5:4. C. a Lewis acid compound selected from the group consisting of zinc nitrate, zinc chloride, magnesium chloride and mixtures thereof, the weight ratio of said Lewis acid compound to said metal acetate being between 1:100 and 1:1. 